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An investigation of sulfate production in clouds using a flow-through chemical reactor model approach

A flow-through chemical reactor model is developed to describe the mass transfer and chemical processes that atmospheric gases undergo in clouds. The model includes the simultaneous absorption of SO2, NH3, O3, NO(x), HNO3, CO2 and H2O2, the accompanying dissociation and oxidation reactions in cloud water, considers electrical neutrality, and includes qualitative parameterization of cloud microphysics. The model is used to assess the importance of the oxidation reactions H2O2-S(IV), O3-S(IV), and S(IV)-Mn(2+) catalysis, and the effects of cloud parameters such as drop size, rain intensity, liquid water content, and updraft velocity. Both precipitating and nonprecipitating clouds are studied. Model results predict sulfate production rates varying from 3 percent/hr to 230 percent/hr. The actual rate is highly dependent on the chemical composition of the uptake air and the physical conditions of the cloud. Model results also show that both the H2O2 and the O3 oxidation reactions can be significant.

Hong, M. S.↗

Instrumentation Working Group Summary

The Instrumentation Working Group compiled a summary of measurement techniques applicable to gas turbine engine aerosol precursors and particulates. An assessment was made of the limits, accuracy, applicability, and technology readiness of the various techniques. Despite advances made in emissions characterization of aircraft engines, uncertainties still exist in the mechanisms by which aerosols and particulates are produced in the near-field engine exhaust. To adequately assess current understanding of the formation of sulfuric acid aerosols in the exhaust plumes of gas turbine engines, measurements are required to determine the degree and importance of sulfur oxidation in the turbine and at the engine exit. Ideally, concentrations of all sulfur species would be acquired, with emphasis on SO2 and SO3. Numerous options exist for extractive and non-extractive measurement of SO2 at the engine exit, most of which are well developed. SO2 measurements should be performed first to place an upper bound on the percentage of SO2 oxidation. If extractive and non-extractive techniques indicate that a large amount of the fuel sulfur is not detected as SO2, then efforts are needed to improve techniques for SO3 measurements. Additional work will be required to account for the fuel sulfur in the engine exhaust. Chemical Ionization Mass Spectrometry (CI-MS) measurements need to be pursued, although a careful assessment needs to be made of the sampling line impact on the extracted sample composition. Efforts should also be placed on implementing non-intrusive techniques and extending their capabilities by maximizing exhaust coverage for line-of-sight measurements, as well as development of 2-D techniques, where feasible. Recommendations were made to continue engine exit and combustor measurements of particulates. Particulate measurements should include particle size distribution, mass fraction, hydration properties, and volatile fraction. However, methods to ensure that unaltered samples are obtained need to be developed. Particulate speciation was also assigned a high priority for quantifying the fractions of carbon soot, PAH, refractory materials, metals, sulfates, and nitrates. High priority was also placed on performing a comparison of particle sizing instruments. Concern was expressed by the workshop attendees who routinely make particulate measurements about the variation in number density measured during in-flight tests by different instruments. In some cases, measurements performed by different groups of researchers during the same flight tests showed an order of magnitude variation. Second priority was assigned to measuring concentrations of odd hydrogen and oxidizing species. Since OH, HO2, H2O2, and O are extremely reactive, non-extractive measurements are recommended. A combination of absorption and fluorescence is anticipated to be effective for OH measurements in the combustor and at the engine exit. Extractive measurements of HO2 have been made in the stratosphere, where the ambient level of OH is relatively low. Use of techniques that convert HO2 to OH for combustor and engine exit measurements needs to be evaluated, since the ratio of HO2/OH may be 1% or less at both the combustor and engine exit. CI-MS might be a viable option for H2O2, subject to sampling line conversion issues. However, H2O2 is a low priority oxidizing species in the combustor and at the engine exit. Two candidates for atomic oxygen measurements are Resonance Enhanced Multi-Photon Ionization (REMPI) and Laser-Induced Fluorescence (LIF). Particulate measurement by simultaneous extractive and non-extractive techniques was given equal priority to the oxidizer measurements. Concern was expressed over the ability of typical ground test sampling lines to deliver an unaltered sample to a remotely located instrument. It was suggested that the sampling probe and line losses be checked out by attempting measurements using an optical or non-extractive technique immediately upstream of the sampling probe. This is a possible application for Laser Induced Incandescence (LII) as a check on the volume fraction of soot. Optical measurements of size distribution are not well developed for ultrafine particles less than about 20 nm in diameter, so a non-extractive technique for particulate size distribution cannot be recommended without further development. Carbon dioxide measurements need to be made to complement other extractive measurement techniques. CO2 measurements enable conversion of other species concentrations to emission indices. Carbon monoxide, which acts as a sink for oxidizing species, should be measured using non-extractive techniques. CO can be rapidly converted to CO2 in extractive probes, and a comparison between extractive and non-extractive measurements should be performed. Development of non-extractive techniques would help to assess the degree of CO conversion, and might be needed to improve the concentration measurement accuracy. Measurements of NO(x) will continue to be critical due to the role of NO and NO2 in atmospheric chemistry, and their influence on atmospheric ozone. Time-resolved measurements of temperature, velocity, and species concentrations were included on the list of desired measurement. Thermocouples are typically adequate for engine exit measurements. PIV and LDV are well established for obtaining velocity profiles. The techniques are listed in the accompanying table; are divided into extractive and non-extractive techniques. Efforts were made to include a measurement uncertainty for each technique. An assessment of the technology readiness was included.

Zaller, Michelle↗

Recent Advances in Hydrogen Peroxide Propulsion Test Capability at NASA's Stennis Space Center E-Complex

In recent years, the rocket propulsion test capability at NASA's John C. Stennis Space Center's (SSC) E-Complex has been enhanced to include facilitization for hydrogen peroxide (H2O2) based ground testing. In particular, the E-3 test stand has conducted numerous test projects that have been reported in the open literature. These include combustion devices as simple as small-scale catalyst beds, and larger devices such as ablative thrust chambers and a flight-type engine (AR2-3). Consequently, the NASA SSC test engineering and operations knowledge base and infrastructure have grown considerably in order to conduct safe H2O2 test operations with a variety of test articles at the component and engine level. Currently, the E-Complex has a test requirement for a hydrogen peroxide based stage test. This new development, with its unique set of requirements, has motivated the facilitization for hydrogen peroxide propellant use at the E-2 Cell 2 test position in addition to E-3. Since the E-2 Cell 2 test position was not originally designed as a hydrogen peroxide test stand, a facility modernization-improvement project was planned and implemented in FY 2002-03 to enable this vertical engine test stand to accomodate H2O2. This paper discusses the ongoing enhancement of E-Complex ground test capability, specifically at the E-3 stand (Cell 1 and Cell 2) and E-2 Cell 2 stand, that enable current and future customers considerable test flexibility and operability in conducting their peroxide based rocket R&D efforts.

Jacks, Thomas E.↗

Coordinate late expression of trefoil peptide genes (pS2/TFF1 and ITF/TFF3) in human breast, colon, and gastric tumor cells exposed to X-rays

The trefoil factors (TFFs) are pleiotropic factors involved in organization and homeostasis of the gastrointestinal tract, estrogen responsiveness, inflammatory disorders, and carcinogenesis. In an earlier study using cDNA array technologies to identify new genes expressed in irradiated cell survivors, we isolated a cDNA clone corresponding to the reported human TFF1 gene (E. K. Balcer-Kubiczek et al., Int. J. Radiat. Biol., 75: 529-541, 1999). To determine whether expression of other TFFs is altered by ionizing radiation, we quantified changes in expression of TFF3 as well as TFF1 in RNA samples obtained from irradiated and control human tumor breast, colon, and gastric tumor cells and examined expression kinetics up to 2 weeks after irradiation. X-ray-induced TFF1 and TFF3 expression profiles were compared with those induced by hydrogen peroxide (H2O2) or 17beta-estradiol (ES). The results revealed that TFF1 and TFF3 mRNA are coinduced by X-irradiation in a subset of the lines, but substantial heterogeneity in their responses was observed in cells derived from a single cell type. TFF1 and TFF3 transcriptional response to X-irradiation differed from that to H2O2 or ES in the timing of their induction as well as tissue-type dependence, i.e., their induction pattern after X-irradiation was late and sustained, whereas their induction by H2O2 or ES was early and transient. TFF1 mRNA, protein production in the cytoplasm, and secretion in the culture supernatant were coordinately regulated after X-irradiation. There was no requirement for TP53 in this induction. These results demonstrate the existence of a novel class of radiation-responsive genes that might be involved in bystander effects.

Non-NASA Center↗

Expanding Hydrogen Peroxide Propulsion Test Capability at NASA's Stennis Space Center E-Complex

In recent years, the rocket propulsion test capability at NASA s John C. Stennis Space Center's (SSC) E-Complex has been enhanced to include facilitization for hydrogen peroxide (H2O2) based ground testing. In particular, the E-3 test stand has conducted numerous test projects that have been reported in the open literature. These include combustion devices as simple at small-scale catalyst beds, and larger devices such as ablative thrust chambers and a flight-type engine (AR2-3). Consequently, the NASA SSC test engineering and operations knowledge base and infrastructure have grown considerably in order to conduct safe H2O2 test operations with a variety of test articles at the component and engine level. Currently, the E-Complex has a test requirement for a hydrogen peroxide based stage test. This new development, with its unique set of requirements, has motivated the facilitization for hydrogen peroxide propellant use at the E-2 Cell 2 test position in addition to E-3. Since the E-2 Cell 2 test position was not originally designed as a hydrogen peroxide test stand, a facility modernization- improvement project was planned and implemented in FY 2002-03 to enable this vertical engine test stand to accommodate H2O2. This paper discusses the ongoing enhancement of E-Complex ground test capability, specifically at the E-3 stand (Cell 1 and Cell 2) and E-2 Cell 2 stand, that enable current and future customers considerable test flexibility and operability in conducting their peroxide based rocket R&D efforts.

Jacks, Thomas E.↗

Improved Electrolytic Hydrogen Peroxide Generator

An improved apparatus for the electrolytic generation of hydrogen peroxide dissolved in water has been developed. The apparatus is a prototype of H2O2 generators for the safe and effective sterilization of water, sterilization of equipment in contact with water, and other applications in which there is need for hydrogen peroxide at low concentration as an oxidant. Potential applications for electrolytic H2O2 generators include purification of water for drinking and for use in industrial processes, sanitation for hospitals and biotechnological industries, inhibition and removal of biofouling in heat exchangers, cooling towers, filtration units, and the treatment of wastewater by use of advanced oxidation processes that are promoted by H2O2.

James, Patrick I.↗

Martian Superoxide and Peroxide O2 Release (OR) Assay: A New Technology for Terrestrial and Planetary Applications

This study presents an assay for the detection and quantification of soil metal superoxides and peroxides in regolith and soil. The O2 release (OR) assay is based on the enzymatic conversion of the hydrolysis products of metal oxides to O2, and their quantification by an O2 electrode based on the stoichiometry of the involved reactions: The intermediate product O2 from the hydrolysis of metal superoxides is converted by cytochrome c to O2, and also by superoxide dismutase (SOD) to 1/2 mol O2 and 1/2 mol H2O2, which is then converted by catalase (CAT) to 1/2 mol O2. The product H2O2 from the hydrolysis of metal peroxides and hydroperoxides is converted to 1/2 mol O2 by CAT. The assay-method was validated in a sealed sample chamber using a liquid-phase Clark-type O2 electrode with known concentrations of O2 and H2O2, and with commercial metal superoxide and peroxide mixed with Mars analogue Mojave and Atacama Desert soils. Carbonates and perchlorates, both present on Mars, do not interfere with the assay. The assay lower limit of detection, using luminescence quenching/optical sensing O2-electrodes, is 1 nmol O2 cm(exp. -3) or better. The activity of the assay enzymes SOD and cytochrome c was unaffected up to 6 Gy exposure by gamma-radiation, while CAT retained 100% and 40% of its activity at 3 and 6 Gy, respectively, demonstrating the suitability of these enzymes for planetary missions, e.g., in Mars or Europa.

soil metal superoxides and peroxides↗

The Influence of Chemical Descriptors on the Reactivity of Potential Hypergolic Fuels With Hydrogen Peroxide

The state-of-the-art for storable hypergolic bipropellant systems is monomethylhydrazine (MMH) and mixed oxides of nitrogen (MON). While MMH and MON provide fast and highly reliable hypergolic ignition with excellent propulsive performance, they suffer from safety concerns impacting their production, cost, and supply to various test and launch facilities. In contrast, identifying and demonstrating low-toxicity fuels hypergolic with rocket grade hydrogen peroxide (H2O2) has been challenging with long ignition delay (IDT) and low propulsive performance affecting their deployment in flight systems. This work describes a preliminary observational study to assess the effects of molecular descriptors suspected to predict the reactivity and hypergolicity of compounds within the same chemical class (i.e., thioamide). The approach centered on evaluating functional groups, electrostatic potential, number of carbons, dipole moment, and adiabatic ionization energy. Thiourea is hypergolic with 89.2 wt.% H2O2 (minimum IDT of 21.9 ms) and was selected as a core fuel to study the reactivity of derived fuels with different functionalities. Additionally, the chemical properties were calculated with the Gaussian16 suite. The results showed that group substitution and generally increased number of carbons on thiourea increases IDT. It was observed that a more positively charged sulfur atom in the thioamide does not increase the reactivity towards H2O2. The dipole moment analysis revealed an overall trend of decreasing IDT due to increasing dipole moment. Finally, a lower adiabatic ionization energy related to increased IDTs for most cases. Additional chemical classes comprising a wider range of functionalities and electrophilic attributes are being investigated in on-going work.

Propellant↗

Elimination of NO Pollutant in Semi-enclosed Spaces over Sodium-promoted Cobalt Oxyhydroxide (CoOOH) by Oxidation and Adsorption Mechanism

Low concentrations of NOx accumulated in air in semi-enclosed spaces is a severe health hazard, but its efficient removal at low cost is a grand challenge. A simple method in preparing CoOOH for low-concentration NO removal at room temperature is described here. The samples are synthesized by oxidizing Co(OH)2 to CoOOH with different oxidants (Na2S2O8, O2 and H2O2). Among them, CoOOH prepared by Na2S2O8 (Co-NS) shows remarkable performance for NO abatement, while the samples synthesized by and H2O2 (Co-HO) and O2 (Co-OG) have no apparent NO removal capacity. It is found that the Co-NS material contains a higher concentration of residual Na, which contributes to the decreased crystallinity and increased concentrations of surface active species (Co2+, active oxygen) for NO storage. Following NO storage, the material can be readily regenerated by water washing. The authors from East China University of Science and Technology acknowledge support from National Basic Research Program of China (2013CB933200), National Natural Science Foundation of China (21577035, 21577034), Commission of Science and Technology of Shanghai Municipality (15DZ1205305) and 111 Project (B08021). Aiyong Wang acknowledges the China Scholarship Council for the Joint-Training Scholarship Program with the Pacific Northwest National Laboratory (PNNL). PNNL is operated by Battelle for the US DOE under contract DE-AC05-76RL01830. FG is supported by the U.S. DOE/Office of Energy Efficiency and Renewable Energy, Vehicle Technologies Office.

NOx abatement, NOx adsorber, ambient temperature, ↗

Data for Selective Oxidation of 3-Hydroxypropionic Acid to Malonic Acid over Pd/C: Mechanistic and Kinetic Study

Malonic acid (MA) is a high-value dicarboxylic acid with strong industrial demand, yet its current production heavily relies on petrochemical feedstocks. Here, we report the first systematic study for the sustainable production of MA via oxidation of 3-hydroxypropionic acid (3-HP) with a Pd/Carbon catalyst. The effects of oxidant type (O2 and H2O2), pH, and temperature on the reaction chemistry were comprehensively evaluated. Guided by experimental observation and DFT-calculated thermochemical energetics, reaction networks for 3-HP oxidation with both oxidants are proposed and validated through kinetic modeling. MA was identified as the primary oxidation product, while further oxidation yields acetic acid and oxalic acid. The kinetic model validated the network, displaying excellent agreement (R2 > 0.95). Kinetic observations also enabled a direct comparison between O2 and H2O2 and revealed their distinct behaviors. The model was further developed into a temperature-time map, providing insight into conditions that maximize MA production. Malonic acid selectivity of 56.9 % and yield of 50.5 % were achieved at 3 bar oxygen, equimolar NaOH:3-HP ratio, and 50 °C.

Bioproducts↗

Data and code from: Selective oxidation of 3-hydroxypropionic acid to malonic acid over Pd/C: Mechanistic and kinetic study

Malonic acid (MA) is a high-value dicarboxylic acid with strong industrial demand, yet its current production heavily relies on petrochemical feedstocks. Here, we report the first systematic study for the sustainable production of MA via oxidation of 3-hydroxypropionic acid (3-HP) with a Pd/Carbon catalyst. The effects of oxidant type (O2 and H2O2), pH, and temperature on the reaction chemistry were comprehensively evaluated. Guided by experimental observation and DFT-calculated thermochemical energetics, reaction networks for 3-HP oxidation with both oxidants are proposed and validated through kinetic modeling. MA was identified as the primary oxidation product, while further oxidation yields acetic acid and oxalic acid. The kinetic model validated the network, displaying excellent agreement (R2 > 0.95). Kinetic observations also enabled a direct comparison between O2 and H2O2 and revealed their distinct behaviors. The model was further developed into a temperature-time map, providing insight into conditions that maximize MA production. Malonic acid selectivity of 56.9 % and yield of 50.5 % were achieved at 3 bar oxygen, equimolar NaOH:3-HP ratio, and 50 °C.

3-Hydroxypropionic Acid↗

Absolute rate constant for the reaction of atomic chlorine with hydrogen peroxide vapor over the temperature range 265-400 K

Rate constants for the reaction of atomic chlorine with hydrogen peroxide were measured from 265-400 K using the flash photolysis-resonance fluorescence technique. Analytical techniques were developed to measure H2O2 under reaction conditions. Due to ambiguity in the interpretation of the analytical results, the data combine to give two equally acceptable representations of the temperature dependence. The results are compared to previous work at 298 K and are theoretically discussed in terms of the mechanism of the reaction. Additional experiments on the H + H2O2 reaction at 298 and 359 K are compared with earlier results from this laboratory and give a slightly revised bimolecular rate constant.

Michael, J. V.↗

Aircraft vortex marking program

A simple, reliable device for identifying atmospheric vortices, principally as generated by in-flight aircraft and with emphasis on the use of nonpolluting aerosols for marking by injection into such vortex (-ices) is presented. The refractive index and droplet size were determined from an analysis of aerosol optical and transport properties as the most significant parameters in effecting vortex optimum light scattering (for visual sighting) and visual persistency of at least 300 sec. The analysis also showed that a steam-ejected tetraethylene glycol aerosol with droplet size near 1 micron and refractive index of approximately 1.45 could be a promising candidate for vortex marking. A marking aerosol was successfully generated with the steam-tetraethylene glycol mixture from breadboard system hardware. A compact 25 lb/f thrust (nominal) H2O2 rocket chamber was the key component of the system which produced the required steam by catalytic decomposition of the supplied H2O2.

Pompa, M. F.↗

Reaction of HO2 with O3 and the effect of water vapor on HO2 kinetics

The effects of temperature and water vapor concentration on the ratio of the rate constant of the reaction HO2 + O3 yields OH + 2(O2) to the square root of the rate constant for the reaction HO2 + HO2 yields H2O2 + O2 are determined. Photolysis of H2-O2-O3 mixtures at 253.7 nm was carried out with H2O pressures in the range 0 to 15 torr at a temperature range of -42.5 to 61 C along with 184.9 nm photolysis of H2O-O2-O3 mixtures. It is shown that the rate of O3 photolysis is suppressed by the addition of water vapor and it is suggested that this effect is realized in the HO2 + HO2 yields H2O2 + O2 reaction. The calculated expression for the temperature dependence of the rate constant ratio is found to be in good agreement with that calculated from separate rate constants. Rate constants determined for the reaction OH + HO2 yields H2O + O2 are found to be higher than those previously determined, presumably due to increased pressure, indicating that atmospheric models should take into account the possible pressure dependences of the reactions considered.

Demore, W. B.↗

I-Xe age and trapped Xe components of the Murray /C-2/ chondrite

A neutron-irradiated bulk sample of the Murray (C-2) carbonaceous chondrite was etched with H2O2 and then divided into colloidal and non-colloidal fractions. The H2O2 treatment removed about 80% of the trapped Xe and greatly increased variations in the Xe-129/Xe-132 ratio measured in stepwise heating. The colloid showed very little excess Xe-129, but the anti-colloid gave a fairly good I-Xe correlation corresponding to formation 3.7 + or - 2.1 m.y. after Bjurbole. Variations in the trapped Xe component were also observed; most notably the 550 C anti-colloid fraction has large deficiencies relative to AVCC at the heavy isotopes.

Niemeyer, S.↗

Intensity of the hydrogen peroxide v6/b/ band around 1266 cm

Laboratory spectra of the V6(b) band of H2O2 at 1266/cm have been obtained at a resolution of 0.06/cm and at temperatures ranging from 278 to 294 K. A total band intensity of 375 + or - 17 per sq cm per amagat is determined from the spectra. Special techniques to handle the H2O2 samples in a way that minimizes abundance determination errors are discussed.

Valero, F. P. J.↗

Ab initio calculation of infrared intensities for hydrogen peroxide

Results of an ab initio SCF quantum mechanical study are used to derive estimates for the infrared intensities of the fundamental vibrations of hydrogen peroxide. Atomic polar tensors (APTs) were calculated on the basis of a 4-31G basis set, and used to derive absolute intensities for the vibrational transitions. Comparison of the APTs calculated for H2O2 with those previously obtained for H2O and CH3OH, and of the absolute intensities derived from the H2O2 APTs with those derived from APTs transferred from H2O and CH3OH, reveals the sets of values to differ by no more than a factor of two, supporting the validity of the theoretical calculation. Values of the infrared intensities obtained correspond to A1 = 14.5 km/mol, A2 = 0.91 km/mol, A3 = 0.058 km/mol, A4 = 123 km/mol, A5 = 46.2 km/mol, and A6 = 101 km/mol. Charge, charge flux and overlap contributions to the dipole moment derivatives are also computed.

Rogers, J. D.↗

The importance of ozone in the oxidation of sulfur dioxide in nonurban tropospheric clouds

In studies of the various possible mechanisms which contribute to the conversion of atmospheric sulfur dioxide to sulfate aerosol in the atmosphere, oxidation within the aqueous, droplet phase of tropospheric clouds has been identified as a major contributor. It has appeared that possibly much of this oxidation is by hydrogen peroxide, with the contribution from ozone being only minimal. The present investigation is concerned with the relative importance of O3 and H2O2 oxidation as a function of pH. The results of a new experimental study of the O3-S(IV) reaction in aqueous solution are presented, and potential S(IV) oxidation rates by O3 in cloud water are compared with those predicted for H2O2. The investigation indicates the potential importance of O3 as a contributor to the overall oxidative conversion of SO2 within typical nonpolluted tropospheric clouds.

Maahs, H. G.↗